A series of new asymmetric bent main-chain liquid crystalline (LC) polyesters (BPE-Cn) were synthesized through the condensation polymerization of A−B type asymmetric α,ω-carboxylic acid−hydroxyl-terminated monomers containing different even numbers of methylene spacers (BPCA-Cn-PmOH, where n = 6, 8, and 10). Differential scanning calorimetry results showed three phase transition processes in this series of BPE-Cn samples. The phase change with the lowest transition temperature is cooling rate dependent, while the two higher temperature transitions are cooling rate independent. One-dimensional (1D) powder wide-angle X-ray diffraction (WAXD) results at different temperatures revealed that during cooling this series of polymers exhibits a low-ordered LC phase and a highly ordered smectic crystal phase before developing a crystalline phase at lower temperatures. The phase structures and symmetry were identified by 2D WAXD and selected area electron diffraction (SAED). On the basis of 2D fiber WAXD patterns, ...